Abstract
Progress in understanding crystallization pathways depends on the ability to unravel relationships between intermediates and final crystalline products at the nanoscale, which is a particular challenge at elevated pressure and temperature. Here we exploit a high-pressure atomic force microscope to directly visualize brucite carbonation in water-bearing supercritical carbon dioxide (scCO2) at 90 bar and 50 °C. On introduction of water-saturated scCO2, in situ visualization revealed initial dissolution followed by nanoparticle nucleation consistent with amorphous magnesium carbonate (AMC) on the surface. This is followed by growth of nesquehonite (MgCO3·3H2O) crystallites. In situ imaging provided direct evidence that the AMC intermediate acts as a seed for crystallization of nesquehonite. In situ infrared and thermogravimetric–mass spectrometry indicate that the stoichiometry of AMC is MgCO3·xH2O (x = 0.5–1.0), while its structure is indicated to be hydromagnesite-like according to density functional theory and X-ray pair distribution function analysis. Our findings thus provide insight for understanding the stability, lifetime and role of amorphous intermediates in natural and synthetic systems.
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All data generated or analysed during this study are included in this published article (and its supplementary information files). Source data for figure plots are available from the authors on request.
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Acknowledgements
We thank M. H. Engelhard and E. Ilton for XPS measurement and data analyses. This material is based on work supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES), Chemical Sciences, Geosciences and Biosciences Division through its Geosciences programme at Pacific Northwest National Laboratory (PNNL). H.T.S. acknowledges support from the DOE Office of Fossil Energy at PNNL through the National Energy Technology Laboratory, Morgantown, West Virginia. The high-pressure AFM, SEM and TEM analyses were performed at the Environmental Molecular Science Laboratory (EMSL), a DOE Office of Science User Facility sponsored by the Office of Biological and Environmental Research and located at PNNL. The high-energy X-ray diffraction and PDF measurements were performed at Beamline 11-ID-B of the Advanced Photon Source (Argonne, IL, United States).
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Contributions
X.Z., J.J.De.Y., H.T.S. and K.M.R. conceived and designed the experiments. X.Z. conducted the AFM experiments and data analysis. X.Z. synthesized the brucite nanodiscs and AMC and performed the ex-situ TEM measurement. A.S.L. and K.M.R. developed the high-pressure AFM and A.S.L. helped to collect the in situ high-pressure imaging data. A.M.C. performed the computer simulation. J.S.L. performed the IR measurements and reacted brucite to AMC for analysis by high-energy XRD, X-ray PDF and TGA–MS measurement. S.T.M. performed the high-energy XRD and X-ray PDF measurements and analysed the data. H.T.S. conducted the X-ray diffraction and TGA–MS measurements. E.N. performed the data analysis on the spatial distribution of the nesquehonite nucleation sites. O.Q. conducted the SEM measurement. X.Z., A.M.C., J.S.L., S.T.M., J.J.De.Y., H.T.S. and K.M.R. cowrote the paper. All authors discussed the results and commented on the manuscript.
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Supplementary information
Supplementary Information
Supplementary Figs. 1–15, Notes 1–16, discussion, description for the video and refs. 1–9.
Supplementary Video 1
In situ high-pressure AFM images from a polished natural brucite crystal surface during exposure to wet scCO2 (water saturated) at 90 bar, 50 °C and a flow rate of 250 µl min−1.
Supplementary Data 1
Computational model of brucite.
Supplementary Data 2
Computational model of hydromagnesite.
Supplementary Data 3
Computational model of Mg-calcium carbonate hemihydrate.
Supplementary Data 4
Computational model of Mg-monohydrocalcite.
Supplementary Data 5
Computational model of nesquehonite.
Supplementary Data 6
Computational model of pokrovskite.
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Zhang, X., Lea, A.S., Chaka, A.M. et al. In situ imaging of amorphous intermediates during brucite carbonation in supercritical CO2. Nat. Mater. 21, 345–351 (2022). https://doi.org/10.1038/s41563-021-01154-5
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DOI: https://doi.org/10.1038/s41563-021-01154-5
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